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Pd-Ag alloy hollow nanostructures with interatomic charge polarization for enhanced electrocatalytic formic acid oxidation

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Abstract

Formic acid oxidation is an important electrocatalytic reaction in protonexchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCOO* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/activation towards improved electrocatalytic performance.

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References

  1. Iyyamperumal, R.; Zhang, L.; Henkelman, G.; Crooks, R. M. Efficient electrocatalytic oxidation of formic acid using Au@Pt dendrimer-encapsulated nanoparticles. J. Am. Chem. Soc. 2013, 135, 5521–5524.

    Article  Google Scholar 

  2. Ma, L.; Wang, C. M.; Gong, M.; Liao, L. W.; Long, R.; Wang, J. G.; Wu, D.; Zhong, W.; Kim, M. J.; Chen, Y. X. et al. Control over the branched structures of platinum nanocrystals for electrocatalytic applications. ACS Nano 2012, 6, 9797–9806.

    Article  Google Scholar 

  3. Zhang, S.; Shao, Y. Y.; Yin, G. P.; Lin, Y. H. Electrostatic self-assembly of a Pt-around-Au nanocomposite with high activity towards formic acid oxidation. Angew. Chem., Int. Ed. 2010, 49, 2211–2214.

    Article  Google Scholar 

  4. Scofield, M. E.; Koenigsmann, C.; Wang, L.; Liu, H. Q.; Wong, S. S. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction. Energy Environ. Sci. 2015, 8, 350–363.

    Article  Google Scholar 

  5. Fu, G. T.; Xia, B. Y.; Ma, R. G.; Chen, Y.; Tang, Y. W.; Lee, J. M. Trimetallic PtAgCu@PtCu core@shell concave nanooctahedrons with enhanced activity for formic acid oxidation reaction. Nano Energy 2015, 12, 824–832.

    Article  Google Scholar 

  6. Zhang, H.; Jin, M. S.; Xia, Y. N. Enhancing the catalytic and electrocatalytic properties of Pt-based catalysts by forming bimetallic nanocrystals with Pd. Chem. Soc. Rev. 2012, 41, 8035–8049.

    Article  Google Scholar 

  7. Jin, M. S.; Zhang, H.; Xie, Z. X.; Xia, Y. N. Palladium nanocrystals enclosed by {100} and {111} facets in controlled proportions and their catalytic activities for formic acid oxidation. Energy Environ. Sci. 2012, 5, 6352–6357.

    Article  Google Scholar 

  8. Mazumder, V.; Sun, S. H. Oleylamine-mediated synthesis of Pd nanoparticles for catalytic formic acid oxidation. J. Am. Chem. Soc. 2009, 131, 4588–4589.

    Article  Google Scholar 

  9. Xia, X. H.; Choi, S. I.; Herron, J. A.; Lu, N.; Scaranto, J.; Peng, H. C.; Wang, J. G.; Mavrikakis, M.; Kim, M. J.; Xia, Y. N. Facile synthesis of palladium right bipyramids and their use as seeds for overgrowth and as catalysts for formic acid oxidation. J. Am. Chem. Soc. 2013, 135, 15706–15709.

    Article  Google Scholar 

  10. Su, N.; Chen, X. Y.; Ren, Y. H.; Yue, B.; Wang, H.; Cai, W. B.; He, H. Y. The facile synthesis of single crystalline palladium arrow-headed tripods and their application in formic acid electro-oxidation. Chem. Commun. 2015, 51, 7195–7198.

    Article  Google Scholar 

  11. Zheng, J. N.; Zhang, M.; Li, F. F.; Li, S. S.; Wang, A. J.; Feng, J. J. Facile synthesis of Pd nanochains with enhanced electrocatalytic performance for formic acid oxidation. Electrochim. Acta 2014, 130, 446–452.

    Article  Google Scholar 

  12. Lu, Y. Z.; Chen, W. Nanoneedle-covered Pd-Ag nanotubes: High electrocatalytic activity for formic acid oxidation. J. Phys. Chem. C 2010, 114, 21190–21200.

    Article  Google Scholar 

  13. Mazumder, V.; Chi, M. F.; Mankin, M. N.; Liu, Y.; Metin, Ö.; Sun, D. H.; More, K. L.; Sun, S. H. A facile synthesis of MPd (M = Co, Cu) nanoparticles and their catalysis for formic acid oxidation. Nano Lett. 2012, 12, 1102–1106.

    Article  Google Scholar 

  14. Wang, Y.; Choi, S. I.; Zhao, X.; Xie, S. F.; Peng, H. C.; Chi, M. F.; Huang, C. Z.; Xia, Y. N. Polyol synthesis of ultrathin Pd nanowires via attachment-based growth and their enhanced activity towards formic acid oxidation. Adv. Funct. Mater. 2014, 24, 131–139.

    Article  Google Scholar 

  15. Hu, S. Z.; Scudiero, L.; Ha, S. Electronic effect of Pd-transition metal bimetallic surfaces toward formic acid electrochemical oxidation. Electrochem. Commun. 2014, 38, 107–109.

    Article  Google Scholar 

  16. Chen, L. Y.; Guo, H.; Fujita, T.; Hirata, A.; Zhang, W.; Inoue, A.; Chen, M. W. Nanoporous PdNi bimetallic catalyst with enhanced electrocatalytic performances for electrooxidation and oxygen reduction reactions. Adv. Funct. Mater. 2011, 21, 4364–4370.

    Article  Google Scholar 

  17. Zhang, Q.; Guo, X.; Liang, Z. X.; Zeng, J. H.; Yang, J.; Liao, S. J. Hybrid PdAg alloy-Au nanorods: Controlled growth, optical properties and electrochemical catalysis. Nano Res. 2013, 6, 571–580.

    Article  Google Scholar 

  18. Zeng, J.; Zhu, C.; Tao, J.; Jin, M. S.; Zhang, H.; Li, Z. Y.; Zhu, Y. M.; Xia, Y. N. Controlling the nucleation and growth of silver on palladium nanocubes by manipulating the reaction kinetics. Angew. Chem., Int. Ed. 2012, 51, 2354–2358.

    Article  Google Scholar 

  19. Fu, G. T.; Liu, C.; Zhang, Q.; Chen, Y.; Tang, Y. W. Polyhedral palladium–silver alloy nanocrystals as highly active and stable electrocatalysts for the formic acid oxidation reaction. Sci. Rep. 2015, 5, 13703.

    Article  Google Scholar 

  20. Yin, Z.; Zhang, Y. N.; Chen, K.; Li, J.; Li, W. J.; Tang, P.; Zhao, H. B.; Zhu, Q. J.; Bao, X. H.; Ma, D. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation. Sci. Rep. 2014, 4, 4288.

    Google Scholar 

  21. Chang, J. F.; Feng, L. G.; Liu, C. P.; Xing, W.; Hu, X. L. An effective Pd-Ni2P/C anode catalyst for direct formic acid fuel cells. Angew. Chem., Int. Ed. 2014, 53, 122–126.

    Article  Google Scholar 

  22. Demirci, U. B. Theoretical means for searching bimetallic alloys as anode electrocatalysts for direct liquid-feed fuel cells. J. Power Sources 2007, 173, 11–18.

    Article  Google Scholar 

  23. Bai, S.; Wang, C. M.; Deng, M. S.; Gong, M.; Bai, Y.; Jiang, J.; Xiong, Y. J. Surface polarization matters: Enhancing the hydrogen-evolution reaction by shrinking Pt shells in Pt–Pd–graphene stack structures. Angew. Chem., Int. Ed. 2014, 53, 12120–12124.

    Article  Google Scholar 

  24. Li, B.; Long, R.; Zhong, X. L.; Bai, Y.; Zhu, Z. J.; Zhang, X.; Zhi, M.; He, J. W.; Wang, C. M.; Li, Z.-Y. et al. Investigation of size-dependent plasmonic and catalytic properties of metallic nanocrystals enabled by size control with HCl oxidative etching. Small 2012, 8, 1710–1716.

    Article  Google Scholar 

  25. Skrabalak, S. E.; Au, L.; Li, X. D.; Xia, Y. N. Facile synthesis of Ag nanocubes and Au nanocages. Nat. Protocols 2007, 2, 2182–2190.

    Article  Google Scholar 

  26. Chen, J. Y.; Wiley, B.; McLellan, J.; Xiong, Y. J.; Li, Z. Y.; Xia, Y. N. Optical properties of Pd-Ag and Pt-Ag nanoboxes synthesized via galvanic replacement reactions. Nano Lett. 2005, 5, 2058–2062.

    Article  Google Scholar 

  27. Zhang, Q.; Cobley, C. M.; Zeng, J.; Wen, L. P.; Chen, J. Y.; Xia, Y. N. Dissolving Ag from Au-Ag alloy nanoboxes with H2O2: A method for both tailoring the optical properties and measuring the H2O2 concentration. J. Phys. Chem. C 2010, 114, 6396–6400.

    Article  Google Scholar 

  28. Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.

    Article  Google Scholar 

  29. Bansal, V.; Li, V.; O'Mullane, A. P.; Bhargava, S. K. Shape dependent electrocatalytic behaviour of silver nanoparticles. CrystEngComm 2010, 12, 4280–4286.

    Article  Google Scholar 

  30. Stamenkovic, V. R.; Mun, B. S.; Arenz, M.; Mayrhofer, K. J. J.; Lucas, C. A.; Wang, G. F.; Ross, P. N.; Markovic, N. M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat. Mater. 2007, 6, 241–247.

    Article  Google Scholar 

  31. Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G. F.; Ross, P. N.; Lucas, C. A.; Markovic, N. M. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 2007, 315, 493–497.

    Article  Google Scholar 

  32. Ji, X. L.; Lee, K. T.; Holden, R.; Zhang, L.; Zhang, J. J.; Botton, G. A.; Couillard, M.; Nazar, L. F. Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. Nat. Chem. 2010, 2, 286–293.

    Article  Google Scholar 

  33. Casado-Rivera, E.; Gál, Z.; Angelo, A. C. D.; Lind, C.; DiSalvo, F. J.; Abruña, H. D. Electrocatalytic oxidation of formic acid at an ordered intermetallic PtBi surface. ChemPhysChem 2003, 4, 193–199.

    Article  Google Scholar 

  34. Venkateswara Rao, C.; Cabrera, C. R.; Ishikawa, Y. Graphene-supported Pt-Au alloy nanoparticles: A highly efficient anode for direct formic acid fuel cells. J. Phys. Chem. C 2011, 115, 21963–21970.

    Article  Google Scholar 

  35. Zhao, Z. Z.; Fang, X.; Li, Y. L.; Wang, Y.; Shen, P. K.; Xie, F. Y.; Zhang, X. The origin of the high performance of tungsten carbides/carbon nanotubes supported Pt catalysts for methanol electrooxidation. Electrochem. Commun. 2009, 11, 290–293.

    Article  Google Scholar 

  36. Arenz, M.; Stamenkovic, V.; Schmidt, T. J.; Wandelt, K.; Ross, P. N.; Markovic, N. M. The electro-oxidation of formic acid on Pt-Pd single crystal bimetallic surfaces. Phys. Chem. Chem. Phys. 2003, 5, 4242–4251.

    Article  Google Scholar 

  37. Wang, H. F.; Liu, Z. P. Formic acid oxidation at Pt/H2O interface from periodic DFT calculations integrated with a continuum solvation model. J. Phys. Chem. C 2009, 113, 17502–17508.

    Article  Google Scholar 

  38. Logadottir, A.; Rod, T. H.; Nørskov, J. K.; Hammer, B.; Dahl, S.; Jacobsen, C. J. H. The Brønsted–Evans–Polanyi relation and the volcano plot for ammonia synthesis over transition metal catalysts. J. Catal. 2001, 197, 229–231.

    Article  Google Scholar 

  39. Bai, S.; Yang, L.; Wang, C. L.; Lin, Y.; Lu, J. L.; Jiang, J.; Xiong, Y. J. Boosting photocatalytic water splitting: Interfacial charge polarization in atomically controlled core–shell cocatalyst. Angew. Chem., Int. Ed. 2015, 54, 14810–14814.

    Article  Google Scholar 

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Authors and Affiliations

  1. Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Hefei Science Center (CAS), and School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, 230026, China

    Dong Liu, Maolin Xie, Chengming Wang, Lu Qiu, Jun Ma, Hao Huang, Ran Long, Jun Jiang & Yujie Xiong

  2. Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, 230021, China

    Lingwen Liao

Authors
  1. Dong Liu
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  2. Maolin Xie
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  4. Lingwen Liao
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  5. Lu Qiu
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  7. Hao Huang
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  9. Jun Jiang
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  10. Yujie Xiong
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Correspondence to Chengming Wang, Jun Jiang or Yujie Xiong.

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These authors contributed equally to this work.

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Liu, D., Xie, M., Wang, C. et al. Pd-Ag alloy hollow nanostructures with interatomic charge polarization for enhanced electrocatalytic formic acid oxidation. Nano Res. 9, 1590–1599 (2016). https://doi.org/10.1007/s12274-016-1053-6

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  • DOI: https://doi.org/10.1007/s12274-016-1053-6

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